Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/882—Molybdenum and cobalt
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/883—Molybdenum and nickel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/888—Tungsten
  • B01J23/8885—Tungsten containing also molybdenum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
  • B01J27/04—Sulfides
  • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
  • B01J27/051—Molybdenum
  • B01J27/0515—Molybdenum with iron group metals or platinum group metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
  • B01J27/19—Molybdenum
• • B01J35/615—
• • B01J35/635—
• • B01J35/647—
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/031—Precipitation
  • B01J37/035—Precipitation on carriers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/16—Reducing
  • B01J37/18—Reducing with gases containing free hydrogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/20—Sulfiding
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
  • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
  • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/888—Tungsten
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/90—Regeneration or reactivation
  • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/28—Regeneration or reactivation
  • B01J27/30—Regeneration or reactivation of catalysts comprising compounds of sulfur, selenium or tellurium
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/70—Catalyst aspects

Definitions

• a hydrotreating catalyst for hydrocarbon cuts is used in order to eliminate the sulfur or nitrogen compounds or aromatic compounds contained therein in order to put for example a petroleum product to the required specifications (sulfur content, content in aromatics etc ..) for a given application (automotive fuel, gasoline or diesel, domestic fuel, jet fuel). It may also be pretreat this cut in order to remove impurities or hydrogenate before subjecting it to various transformation processes to modify the physicochemical properties, such as for example reforming processes, d hydrocracking of vacuum distillates, catalytic cracking, hydroconversion of atmospheric residues or under vacuum.
• composition and use of hydrotreatment catalysts are particularly well described in the article of the book Catalysis by Transition Metal Sulphides, From Molecular Theory to Industrial Application, by RAYBAUD Pascal and TOULHOAT Hervé, published by Technip.
• the hardening of automobile pollution standards in the European community ( Official Journal of the European Union, L76, 22 March 2003, Directive 2003/70 / EC, pages L76 / 10-L76 / 19 ) Has forced refiners to dramatically reduce the sulfur content in diesel fuel and gasoline (at most 10 parts per million by weight (ppm) of sulfur at 1 January 2009, against 50 ppm to 1 January 2005) and Similar standards have been or will be implemented gradually around the world.
• Conventional hydrotreatment catalysts generally comprise a support based on at least one oxide of a metal or metalloid and an active phase based on metals of groups VIB and VIII in their oxide forms and optionally a doping element such as phosphorus.
• the preparation of these catalysts generally comprises a step of impregnating the metals and phosphorus on the support, followed by drying and optionally calcination to obtain the active phase in its oxide form. In some cases, they may also include presence during their preparation of organic additives.
• the catalytic precursors are generally subjected to a sulphidation step in order to convert the metal oxides to sulphides.
• This step makes it possible to transform the catalytic precursor obtained by any of the preparation methods known to those skilled in the art into a sulphurized catalyst in order to form its active species. It is also a necessary step for the activation of the regenerated catalysts. This activation or sulphurization step is also very well known by those skilled in the art. Many sulfurization processes have been described in the state of the art. In practice, liquid phase sulphurization processes are distinguished from those in the gas phase. For so-called liquid phase processes, the catalytic precursor is treated, in the presence of hydrogen, by means of a liquid phase (generally a liquid hydrocarbon such as a gas oil) comprising sulfur compounds.
• a liquid phase generally a liquid hydrocarbon such as a gas oil
• EP 130850 , EP 0785022 or US 4,530,917 in which the sulphiding agent is introduced by impregnation into the catalyst in oxide form prior to the activation step conventionally carried out.
• patent application FR 2706326 which claims the use of two sulfur compounds, the former being similar to those mentioned above and the second more difficult to decompose is used specifically at higher temperatures.
• the patent application EP 0064429 sets certain rules to optimize the sulphidation, and in particular the implementation of sulphurations in temperature increments. For so-called gas phase processes, the catalyst is treated with a gaseous mixture containing sulfur (most of the time, hydrogen sulphide).
• a catalytic precursor sulphurization process which comprises contacting said catalytic precursor in the presence of hydrogen with an at least partially hydrotreated hydrocarbon fraction and a sulfur compound.
• an at least partially hydrotreated hydrocarbon fraction and a sulfur compound other than those present in the hydrocarbon fraction chosen makes it possible to sulphide the catalytic precursor more rapidly and / or, for the same sulphurization time, to conduct a catalyst that is generally more active than those conventionally obtained by the sulphurization processes known to the human being. profession, by example in the presence of a non-hydrotreated hydrocarbon fraction and a sulfur compound.
• the invention relates to a process for the sulphidation of a catalytic precursor comprising a support on which at least one Group VIB metal and at least one Group VIII metal are deposited, in which, in the presence of hydrogen, they are brought into contact with each other.
• said precursor with a hydrotreated hydrocarbon fraction comprising at least 90% by weight of hydrocarbon compounds whose boiling temperature is between 30 ° C and 520 ° C at atmospheric pressure and a sulfur compound added to said hydrotreated hydrocarbon fraction, the content of added sulfur being between 0.2 and 6% by weight relative to the weight of the hydrotreated hydrocarbon fraction, said sulphurization process being carried out at a temperature of between 150 and 400 ° C., at a total pressure of between 1 and 15 MPa, with a hourly volume velocity (VVH) of between 0.1 h -1 and 5 h -1 and with a volume ratio between the total hydrogen flow rate and the flow rate of the cut hydrotreated hydrocarbon between 30 and 1400 Nl / l.
• VVH hourly volume velocity
• At least one sulfurization stage is carried out at a temperature of between 150 and 400 ° C.
• the total pressure is between 1.5 and 14.5 MPa and the volume ratio between the total flow of hydrogen and the flow rate of the hydrotreated hydrocarbon fraction is between 50 and 1000 Nl / l.
• the hydrotreated hydrocarbon feedstock has a sulfur content of less than 5000 ppm by weight and a nitrogen content of less than 300 ppm by weight, based on the total weight of the hydrotreated hydrocarbon fraction.
• the hydrotreated hydrocarbon fraction is chosen from gasoil, kerosene, gasoline or vacuum distillate fractions, taken alone or as a mixture.
• the hydrotreated hydrocarbon fraction is a gas oil fraction having at least 90% of the compounds whose boiling point is between 250 ° C. and 400 ° C. at atmospheric pressure and a sulfur content of between 0.degree. 1 and 3000 ppm weight.
• the hydrotreated hydrocarbon fraction is a gasoline fraction comprising at least 90% by weight of compounds whose boiling point is between 30 and 260 ° C. at atmospheric pressure and a sulfur content of between 0.1. and 1000 ppm weight.
• the hydrotreated hydrocarbon fraction is a vacuum distillate fraction having at least 80% by weight of hydrocarbon compounds whose boiling point is greater than 340 ° C. at atmospheric pressure and a sulfur content of between 0.degree. 1 and 5000 ppm weight.
• the sulfur compound added and used is chosen from elemental sulfur, carbon disulfide (CS 2 ), sulfur-containing organic compounds such as mercaptans, sulphides, disulfides, polysulfides, thiophenes, sulfoxides, taken alone or as a mixture.
• CS 2 carbon disulfide
• sulfur-containing organic compounds such as mercaptans, sulphides, disulfides, polysulfides, thiophenes, sulfoxides, taken alone or as a mixture.
• the catalytic precursor comprises a support based on alumina or silica or silica-alumina, at least one group VIB metal with a content expressed in oxide of between 3 and 40% by weight, and less a group VIII metal with a content expressed in oxide of between 0.5 and 10% by weight, relative to the total weight of the catalytic precursor.
• the catalytic precursor comprises at least one doping element chosen from phosphorus, boron, and fluorine and / or at least one organic compound that can be used during the preparation of the catalytic precursor.
• the Group VIB metal is selected from molybdenum and tungsten and the Group VIII metal is selected from cobalt and nickel.
• the metals of group VIB and VIII are chosen from cobalt-molybdenum, nickel-molybdenum, nickel-tungsten or nickel-cobalt-molybdenum, or nickel-molybdenum-tungsten combinations.
• Another subject of the present invention relates to the catalyst obtained by the sulfurization process according to the invention.
• Another subject of the present invention relates to the process for hydrotreatment of a hydrocarbon feedstock using a sulphurized catalyst by the process according to the invention, the hydrotreatment process being carried out at a temperature of between 180 and 450.degree. ° C, at a pressure of between 0.5 and 30 MPa, with an hourly space velocity of between 0.1 and 20 h -1 and with a volume ratio of hydrogen to hydrocarbon feed of between 50 and 5000 nl / l.
• the groups of chemical elements are given according to the CAS classification ( CRC Handbook of Chemistry and Physics, Editor CRC Press, Editor-in-Chief DR Lide, 81st Edition, 2000-2001 ).
• the group VIII according to the CAS classification corresponds to the metals in columns 8, 9 and 10 according to the new IUPAC classification.
• the present invention relates to a process for the sulfurization of a catalytic precursor comprising a support on which at least one Group VIB metal and at least one Group VIII metal are deposited, in which, in the presence of hydrogen, said precursor is brought into contact with a hydrotreated hydrocarbon fraction comprising at least 90% by weight of hydrocarbon compounds whose boiling point is between 30 ° C. and 520 ° C.
• a catalyst is considered to be sulphurized when the molar ratio between the sulfur (S) present on the catalyst and the metals is greater than 60% of the theoretical molar ratio corresponding to the total sulphidation of the metals.
• the sulfurization process according to the invention is of the liquid type and can be carried out in situ or ex situ, that is to say in or out of the hydrotreatment reactor in which the catalyst in sulphurized form is then put into operation. artwork.
• At least one sulfurization stage is carried out at a temperature of between 150 and 400 ° C, preferably between 200 and 350 ° C, and very preferably between 250 and 330 ° C.
• the duration of said plateau is sufficiently long to reach the piercing of H 2 S in the effluent recovered at the outlet of the sulfurization reactor.
• the ramp (s) temperature (s) is (are) generally between 1 ° C per hour and 50 ° C per hour, preferably between 5 ° C per hour and 30 ° C per hour.
• the sulphurization is carried out in two stages, an intermediate stage, and a final stage.
• the duration of the final stage is between 0.5 and 24 hours, preferably between 2 and 12 hours.
• the hourly volume velocity (VVH) is generally between 0.1 h -1 and 5 h -1 , preferably between 0.3 h -1 and 3 h -1 and very preferably between 0.5 h - 1 and 2 h -1 .
• the hourly volume velocity (VVH) may be set throughout the sulfurization or may be increased gradually, or changed as many times as it is deemed necessary by the skilled person or that the industrial unit requires.
• the total pressure is between 1 and 15 MPa, preferably between 1.5 and 14.5 MPa, and very preferably between 2.5 and 14 MPa.
• the volume ratio (at the reactor inlet) between the total flow rate of hydrogen and the flow rate of the hydrotreated hydrocarbon fraction is between 30 and 1400 Nl / l, preferably between 50 and 1000 Nl / l and very preferred between 100 and 800 Nl / l.
• the hydrogen flow rate is defined under normal conditions of pressure and temperature.
• the contents of sulfur (S), nitrogen (N) and aromatic are measured according to ASTDM D-4294, ASTDM D-5291, ASTDM D-5186 respectively.
• the hydrocarbon fraction used is hydrotreated beforehand so as to reduce by at least 50% its sulfur content relative to that before hydrotreatment, preferably at least 80% and very preferably from at least 90%.
• the hydrotreated hydrocarbon fraction comprises at least 90% by weight of hydrocarbon compounds whose boiling point is between 30 ° C. and 520 ° C. at atmospheric pressure.
• the hydrotreated hydrocarbon fraction has a nitrogen content of less than 300 ppm by weight.
• this content is between 1 and 300 ppm by weight, more preferably between 1 and 200 ppm by weight, and very preferably between 1 and 100 ppm by weight relative to the total weight of the hydrotreated hydrocarbon fraction.
• the hydrotreated hydrocarbon fraction has a sulfur content of less than 5000 ppm by weight, relative to the total weight of the hydrotreated hydrocarbon fraction.
• Said sulfur content is generally between 0 and 3000 ppm by weight relative to the total weight of the hydrotreated hydrocarbon fraction, preferably between 0.1 and 1000 ppm by weight, preferably between 1 and 500 ppm, more preferably between 8 and 300 ppm and very preferably between 8 and 200 ppm by weight relative to the total weight of the hydrotreated hydrocarbon fraction.
• the hydrotreated hydrocarbon fraction has an aromatic compound content of less than 40% by weight, relative to the total weight of the hydrotreated hydrocarbon fraction, and preferably less than 30% by weight.
• the content of polyaromatic compounds containing at least three aromatic rings is between 0 and 0.5% by weight and very preferably between 0 and 0.2% by weight relative to the total weight of the cup. hydrotreated hydrocarbon.
• a content of di-aromatic compounds of less than 10% by weight, preferably less than 8% by weight and even more preferably less than 6% by weight relative to the total weight of the hydrotreated hydrocarbon fraction will be preferred.
• the hydrotreated hydrocarbon fraction is chosen from gasoil, kerosene, gasoline or vacuum distillate fractions, taken alone or as a mixture.
• the hydrotreated hydrocarbon fraction used is a hydrotreated effluent from the unit for which the catalyst in sulphurized form will be used, possibly after a fractionation step.
• the hydrotreated hydrocarbon fraction is a hydrotreated gas oil fraction comprising at least 90% by weight of compounds whose boiling point is between 250 ° C. and 400 ° C. at atmospheric pressure and whose sulfur is between 0.1 and 3000 ppm by weight.
• the sulfur content is between 5 and 1000 ppm by weight, more preferably between 8 and 500 ppm by weight and very preferably between 10 and 300 ppm by weight relative to the total weight of the hydrotreated hydrocarbon fraction.
• the diesel cut may be derived from a coking unit (coking according to the English terminology), a visbreaking unit (visbreaking according to the English terminology), a steam cracking unit (according to the terminology). Anglo-Saxon), a hydroprocessing unit and / or hydrocracking of heavier cuts and / or a catalytic cracking unit (Fluid Catalytic Cracking according to the English terminology).
• the corresponding hydrocarbon fraction before hydrotreatment is a diesel cut from the direct distillation of oil (or Straight Run Gasoil according to the English terminology).
• the hydrotreated hydrocarbon fraction is a hydrotreated gasoline fraction having a sulfur content of between 0.1 and 1000 ppm by weight relative to the total weight of the hydrotreated hydrocarbon fraction, preferably between 0.1 and 500 ppm weight. More preferably, the sulfur content in the hydrotreated gasoline cutter is included between 5 and 300 ppm by weight and very preferably between 8 ppm and 100 ppm by weight.
• Said gasoline cut comprises at least 90% by weight of compounds whose boiling point is between 30 and 260 ° C at atmospheric pressure.
• the gasoline cut before hydrotreatment is directly derived from atmospheric distillation, but it can also act as an olefinic gasoline cut resulting for example from a catalytic cracking unit (Fluid Catalytic Cracking). .
• the hydrotreated hydrocarbon fraction is a "heavy" hydrocarbon fraction of the vacuum distillate type, which contains at least 20% by weight and often at least 80% by weight of hydrocarbon compounds whose boiling point is greater than 340 ° C at atmospheric pressure.
• the cuts have a boiling point T5, measured by the ASTM D86 method, greater than 340 ° C. at atmospheric pressure and preferably greater than 370 ° C. at atmospheric pressure, that is to say that 95% by weight of
• the compounds present in the cup have a boiling point above 340 ° C, and more preferably above 370 ° C.
• the sulfur content of these hydrocarbon fractions of the vacuum distillate type is generally between 0.1 and 5000 ppm by weight, preferably between 30 and 1000 ppm by weight, and very preferably between 50 ppm and 200 ppm by weight.
• the hydrocarbon fraction contains only low levels of metals (for example nickel and vanadium), and in particular the measured content is less than 1 ppm by weight.
• the asphaltene content is generally less than 1000 ppm by weight.
• the "heavy" hydrocarbon fraction can be chosen from a distillate obtained from vacuum distillation, or a section from aromatic extraction units of lubricating oil bases or derived from solvent dewaxing of lubricating oil bases. and / or deasphalted oils.
• the hydrocarbon fraction can also be a deasphalted oil or paraffins from the Fischer-Tropsch process or any mixture of the previously mentioned sections.
• the sulfur compounds used in the process according to the invention are chosen from elemental sulfur, carbon disulfide (CS 2 ), sulfur-containing organic compounds such as mercaptans, sulphides, disulfides, polysulfides, thiophenes, sulfoxides, taken alone or as a mixture.
• the sulfur compound has the ability to decompose to give rise to hydrogen sulfide (H 2 S), which in the presence of hydrogen will lead to the desired sulfides of the metals present in the catalytic precursor.
• the sulfur compound is added to the hydrotreated hydrocarbon fraction so that the amount of sulfur added is between 0.2 and 6% by weight relative to the weight of the hydrotreated hydrocarbon fraction, preferably between 0.4 and 4%. weight, very preferably between 0.5 and 3% by weight
• the preferred disulfide is dimethyl disulfide.
• the preferred alkyl sulfide is, for example, dimethyl sulfide.
• the polysulfides that can be used correspond to the following formulation: RS (n) -R ' in which n is between 3 and 7 and wherein the groups R and R 'are organic radicals comprising from 1 to 30 carbon atoms and are chosen from among saturated or unsaturated, linear or branched alkyls, naphthenic rings, aryls. alkylaryls or arylalkyls and may contain one or more heteroatoms.
• ditertiododecylpolysulfide or ditertiononylpolysulfide (n 5) is mentioned.
• the preferred mercaptan type sulfur compound is n-butyl mercaptan (or 1-butanethiol).
• the support is advantageously in the form of balls, extrudates, pellets, or irregular and non-spherical agglomerates whose specific shape can result from a crushing step.
• the support may be based on alumina or silica or silica-alumina.
• the support When the support is based on alumina, it contains more than 50% by weight of alumina with respect to the total weight of the support. Preferably the support contains only alumina. Preferably, the alumina is gamma alumina.
• the alumina support advantageously has a total pore volume of between 0.1 and 1.5 cm 3 .g -1 , preferably between 0.4 and 1.1 cm 3 .g -1 . The total pore volume is measured by mercury porosimetry according to standard ASTM D4284 with a wetting angle of 140 °, as described in the book Rouquerol F .; Rouquerol J .; Singh K.
• the specific surface of the alumina support is advantageously between 5 and 400 m 2 .g -1 , preferably between 10 and 350 m 2 .g -1 , more preferably between 40 and 350 m 2 .g -1 .
• the specific surface is determined in the present invention by the BET method according to ASTM D3663, known to those skilled in the art.
• the support of said catalyst is a silica-alumina containing at least 50% by weight of alumina with respect to the total weight of the support.
• the silica content in the support is at most 50% by weight relative to the total weight of the support, most often less than or equal to 45% by weight, preferably less than or equal to 40% by weight.
• the support of said catalytic precursor is based on silica, it contains more than 50% by weight of silica relative to the total weight of the support. According to one embodiment, the support contains only silica.
• the support consists of alumina, silica or silica-alumina.
• the support may also advantageously contain from 0.1 to 50% by weight of zeolite.
• all sources of zeolite can be incorporated in said support.
• the zeolite is chosen from the group FAU, BEA, ISV, IWR, IWW, MEI, UWY and very preferably, the zeolite is chosen from the group FAU and BEA, such as zeolite Y and / or beta.
• the support may also comprise at least one metal chosen from a group VIB and VIII metal, and / or at least one doping element chosen from phosphorus, boron, and fluorine and / or at least one organic compound which can be used during the preparation of the catalytic precursor.
• Preferred Group VIB metals are molybdenum and tungsten.
• the preferred Group VIII metals are non-noble metals and in particular cobalt and nickel.
• said preferred metals are chosen from cobalt-molybdenum, nickel-molybdenum, nickel-tungsten or nickel-cobalt-molybdenum, or nickel-molybdenum-tungsten combinations.
• the total content of Group VIB and Group VIII metals is advantageously greater than 3.5% by weight, expressed as oxide relative to the total weight of the catalytic precursor.
• the molar ratio of Group VIII metal to Group VIB metal in the catalyst is preferably between 0.1 and 0.8, preferably between 0.15 and 0.6 and even more preferably between 0.2 and 0.5.
• the catalytic precursor comprises phosphorus.
• the phosphorus content is between 0.1 and 20% by weight, expressed as P 2 O 5 , preferably between 0.2 and 15% by weight expressed as P 2 O 5 , and very preferably between 0.3% by weight.
• 10% by weight expressed as P 2 O 5 relative to the total weight of the catalytic precursor and the ratio of phosphorus to metal of group VIB in the catalytic precursor is greater than or equal to 0.05, preferably greater than or equal to 0.07, preferably between 0.08 and 1, preferably between 0.08 and 0.7 and very preferably between 0.08 and 0.5.
• the catalytic precursor has been prepared using one or more organic compounds containing oxygen and / or nitrogen and / or sulfur.
• the organic compound is chosen from a compound comprising one or more chemical functional groups chosen from a carboxylic function, alcohol, thiol, thioether, sulphone, sulphoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime , urea and amide.
• the organic compound is chosen from dimethyl succinate, ⁇ -valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid, 4-pentenoic acid and ⁇ -acid.
• -cetovaleric triethylene glycol, diethylene glycol, ethylenediaminetetraacetic acid (EDTA), maleic acid, citric acid, dimethylformamide, bicine, tricine, 2-acetylbutyrolactone, 2- (2-hydroxyethyl) -3-oxobutanoic acid, 3-hydroxy-2- (2-hydroxyethyl) -2-butenoic acid, 2-methoxyethyl 3-oxobutanoate or 2-methacryloyloxyethyl 3-oxobutanoate.
• EDTA ethylenediaminetetraacetic acid
• Another subject of the invention relates to the use of the sulphurized catalyst by the process according to the invention in processes for hydrotreatment and / or hydrocracking of hydrocarbon feeds.
• the catalyst obtained by the sulfurization process according to the invention is advantageously used for the hydrotreatment and / or hydrocracking reactions of hydrocarbon feedstocks such as petroleum cuts, cuts from coal or hydrocarbons produced from natural gas, possibly in mixtures or hydrocarbon cuts derived from biomass.
• the sulfurized catalysts according to the invention are used in hydrogenation, hydrodenitrogenation, hydrodearomatization, hydrodesulfurization, hydrodeoxygenation, hydrodemetallation or hydroconversion reactions of hydrocarbon fractions.
• the hydrocarbon feedstocks treated in the hydrotreatment process are, for example, gasolines, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuels, oils and the like. , waxes and paraffins, waste oils, residues or deasphalted crudes, cuts resulting from thermal or catalytic conversion processes, lignocellulosic cuts or more generally cuts from biomass, taken alone or as a mixture.
• the hydrocarbon feeds that are treated, and in particular those mentioned above generally contain heteroatoms such as sulfur, oxygen and nitrogen and, for heavy cuts, they most often also contain metals.
• the hydrocarbon feedstock is for example a hydrocarbon cut having a distillation range of between 30 and 400 ° C.
• this hydrocarbon feedstock is a diesel type cut or an olefin gasoline type cut from a catalytic cracking unit (Fluid Catalytic Cracking).
• the operating conditions used in the processes employing the hydrocarbon cutting hydrotreatment reactions described above are generally as follows: the temperature is generally between 180 and 450 ° C., and preferably between 250 and 440 ° C., pressure is generally between 0.5 and 30 MPa, and preferably between 1 and 18 MPa, the hourly volume rate is generally between 0.1 and 20 h -1 and preferably between 0.2 and 5 h -1 , and with a ratio a ratio between the hydrogen flow rate and the flow rate of the hydrocarbon feedstock of between 50 to 5000 Nl / l and preferably between 80 to 2000 Nl / l.
• said hydrotreatment process according to the invention is a hydrotreatment process, in particular hydrodesulfurization (HDS), a petrol or gas oil cut made in the presence of at least one sulfurized catalyst according to the invention.
• HDS hydrodesulfurization
• Said hydrotreatment process aims at eliminating the sulfur compounds present in said gasoline or diesel fuel cut in order to reach the environmental standards in force, namely a permissible sulfur content of up to 10 ppm. It advantageously also makes it possible to reduce the aromatics and nitrogen contents of the diesel fraction to be hydrotreated.
• the F1 section is obtained by pretreatment in a fixed bed of a gasoil section corresponding to the section F2.
• Said cut F2 is identical to the diesel fraction used during the hydrodesulfurization tests described in Example 3.
• alumina support having a BET surface area of 230 m 2 / g, a pore volume obtained by mercury porosimetry of 0.78 ml / g and an average pore diameter of 11.5 nm defined as the median diameter by volume by mercury porosimetry and which is in the form "extruded", cobalt, molybdenum and phosphorus are added.
• the impregnating solution is prepared by dissolving 90 ° C. of molybdenum oxide (24.34 g) and cobalt hydroxide (5.34 g) in 7.47 g of a phosphoric acid solution. 85% in water.
• the dried catalyst precursor thus obtained is denoted C1.
• Sulfurization of the catalytic precursor C1 is conducted in a fixed bed type reactor.
• a single temperature ramp of 16 ° C per hour was applied, with a hourly volume velocity (VVH) of 0.5 h -1 .
• the total pressure applied is 3 MPa and the volume ratio between the hydrogen and the hydrocarbon fraction (hydrotreated or non-hydrotreated) is 150 Nl / l at the reactor inlet.
• the final bearing temperature was set at 300 ° C and the duration was varied for each procedure / cut between 2 hours, 4 hours, 8 hours and 12 hours
• the first sulfurization procedures not according to the invention use the F2 cut and no additional sulfurization additive.
• the second sulfurization procedures not according to the invention denoted P9, P10, P11, and P12 use said F2 cut to which is added 2% by weight of dimethyl disulfide (DMDS), bringing the overall sulfur content of the F2 cut at 2.72% weight.
• DMDS dimethyl disulfide
• the hydrodesulfurization tests are carried out on the F2 section in a fixed-bed isothermal pilot reactor, the fluids flowing from bottom to top.
• the hydrodesulfurization reaction was carried out under the following operating conditions: a total pressure of 3 MPa, a catalyst volume of 30 cm 3 , a temperature of 330 to 360 ° C, a cutting rate of 30 cm 3 / h corresponding at a speed volume hourly (VVH) of 1h -1 and with a hydrogen flow rate of 24 l / h, a volume ratio between hydrogen and the F2 cut of 240 Nl / l.
• the catalytic hydrodesulphurization performances of the catalysts obtained by the different sulphurization procedures are given in Table 3. They are expressed in degrees Celsius with respect to a sulphurized catalyst according to a sulphurization procedure not in accordance with the invention chosen as reference and correspond to the difference in temperature to be applied to reach 50 ppm of sulfur in the effluent.
• a negative temperature difference from the reference catalyst means that the sulfur target is reached for a lower temperature and thus there is a gain in activity.
• a positive temperature difference value means that the target of sulfur content is reached for a higher temperature and that there is therefore a loss of activity.
• Table 3 Iso-volume activity in hydrodesulfurization (HDS) of diesel sulphide catalysts Sulphidation procedure catalysts Duration of the sulfurization stage (hours) HDS activity true C (P1) 2 Base + 0.2 ° C true C (P2) 4 Base - 0.3 ° C true C (P3) 8 Base - 0.8 ° C true C (P4) 12 Base -1 ° C Improper C (P5) 2 Base + 5.1 ° C Improper C (P6) 4 Base + 3.5 ° C Improper C (P7) 8 Base + 1.2 ° C Improper C (P8) 12 Based Improper C (P9) 2 Base + 1.5 ° C Improper C (P10) 4 Base + 0.5 ° C Improper C (P11) 8 Base + 0.2 ° C Improper C (P12) 12 Base - 0.3 ° C
• the activity of catalyst C (P8) serves as a reference base for evaluating the activity of the other catalysts used in the hydrodesulfurization reaction.
• the activity of the catalysts during the hydrodesulphurization reaction is representative of the efficiency of the process for sulphurizing catalytic precursors.
• the catalyst C (P1) activated by the process according to the invention, using 2 hours of final sulfurization stage, has a hydrodesulphurization activity comparable to that of catalysts C (P8) and C (P11) which respectively underwent 12 hours. and 8 hours of final sulfurization stage.

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